(1S,3aR,4S,5R,7aS)-1-Ethyl-5-<2-(trimethylsilyl)ethynyl>-4-(2-pyrrolylcarbonyl)-2,3,3a,4,5,7a-hexahydro-1H-indene | 153868-83-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,3aR,4S,5R,7aS)-1-Ethyl-5-<2-(trimethylsilyl)ethynyl>-4-(2-pyrrolylcarbonyl)-2,3,3a,4,5,7a-hexahydro-1H-indene
• 英文别名: [(1S,3aR,4S,5R,7aS)-1-ethyl-5-(2-trimethylsilylethynyl)-2,3,3a,4,5,7a-hexahydro-1H-inden-4-yl]-(1H-pyrrol-2-yl)methanone
• CAS: 153868-83-8
• 化学式: C₂₁H₂₉NOSi
• 分子量: 339.553
• InChiKey: KERUYSIMWFLDFE-WRMBXCAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.93
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  32.9
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,3aR,4S,5R,7aS)-1-Ethyl-5-<2-(trimethylsilyl)ethynyl>-4-(2-pyrrolylcarbonyl)-2,3,3a,4,5,7a-hexahydro-1H-indene 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以98%的产率得到(1S,3aR,4S,5R,7aS)-1-Ethyl-5-ethynyl-4-(2-pyrrolylcarbonyl)-2,3,3a,4,5,7a-hexahydro-1H-indene
  参考文献：
  名称：

  Total synthesis of ionophore antibiotic X-14547 A (indanomycin)

  摘要：

  A convergent, enantioselective total synthesis of ionophore antibiotic X-14547A (indanomycin, 1) is described. The dioxanone-to-dihydropyran variant of the lactonic Ireland-Claisen rearrangement establishes the hydropyran nucleus of the ''left wing'' fragment 2. Elaboration to the target synthon utilizes a new methodology for the preparation of stereodefined vinylsilanes (24 --> 25 --> 26) via net S(N)2' coupling of [alpha-(mesyloxy)allyl]silanes with Grignard reagents catalyzed by CuCN. Salient features in the construction of the ''right wing'' subunit 3 include a modification of the Noyori three-component coupling procedure (32 --> 33) and the application,of a retro hetero Diels-Alder/intramolecular Diels-Alder (''mock Claisen'') process (5 --> 39), Palladium-mediated cross Coupling of ''left wing'' and ''right wing'' synthons using Stille's method tolerates a free carboxylic acid and an unprotected acyl pyrrole, affording indanomycin directly in its natural absolute configuration.

  DOI：

  10.1021/jo00081a010
• 作为产物：
  描述：

  tert-Butyl <(1S,2R,3S)-3-ethyl-2-phenylcyclopent-1-yl>acetate 在 trans-benzyl(chloro)-bis(triphenylphosphine)palladium(II) 、 N,N-二甲基甲酰胺 4-二甲氨基吡啶 、 ruthenium trichloride 、 sodium hydroxide 、 sodium tetrahydroborate 、 sodium periodate 、 cerium(III) chloride 、 草酰氯 、 达卡巴嗪 、 三乙胺 、 三苯基膦 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 98.75h， 生成 (1S,3aR,4S,5R,7aS)-1-Ethyl-5-<2-(trimethylsilyl)ethynyl>-4-(2-pyrrolylcarbonyl)-2,3,3a,4,5,7a-hexahydro-1H-indene
  参考文献：
  名称：

  Total synthesis of ionophore antibiotic X-14547 A (indanomycin)

  摘要：

  A convergent, enantioselective total synthesis of ionophore antibiotic X-14547A (indanomycin, 1) is described. The dioxanone-to-dihydropyran variant of the lactonic Ireland-Claisen rearrangement establishes the hydropyran nucleus of the ''left wing'' fragment 2. Elaboration to the target synthon utilizes a new methodology for the preparation of stereodefined vinylsilanes (24 --> 25 --> 26) via net S(N)2' coupling of [alpha-(mesyloxy)allyl]silanes with Grignard reagents catalyzed by CuCN. Salient features in the construction of the ''right wing'' subunit 3 include a modification of the Noyori three-component coupling procedure (32 --> 33) and the application,of a retro hetero Diels-Alder/intramolecular Diels-Alder (''mock Claisen'') process (5 --> 39), Palladium-mediated cross Coupling of ''left wing'' and ''right wing'' synthons using Stille's method tolerates a free carboxylic acid and an unprotected acyl pyrrole, affording indanomycin directly in its natural absolute configuration.

  DOI：

  10.1021/jo00081a010

文献信息

• Total synthesis of ionophore antibiotic X-14547 A (indanomycin)
  作者：Steven D. Burke、Anthony D. Piscopio、Michael E. Kort、Mark A. Matulenko、Marshall H. Parker、David M. Armistead、K. Shankaran

  DOI：10.1021/jo00081a010

  日期：1994.1

  A convergent, enantioselective total synthesis of ionophore antibiotic X-14547A (indanomycin, 1) is described. The dioxanone-to-dihydropyran variant of the lactonic Ireland-Claisen rearrangement establishes the hydropyran nucleus of the ''left wing'' fragment 2. Elaboration to the target synthon utilizes a new methodology for the preparation of stereodefined vinylsilanes (24 --> 25 --> 26) via net S(N)2' coupling of [alpha-(mesyloxy)allyl]silanes with Grignard reagents catalyzed by CuCN. Salient features in the construction of the ''right wing'' subunit 3 include a modification of the Noyori three-component coupling procedure (32 --> 33) and the application,of a retro hetero Diels-Alder/intramolecular Diels-Alder (''mock Claisen'') process (5 --> 39), Palladium-mediated cross Coupling of ''left wing'' and ''right wing'' synthons using Stille's method tolerates a free carboxylic acid and an unprotected acyl pyrrole, affording indanomycin directly in its natural absolute configuration.